BENZO{8 b{9 PYRYLIUM DYE SALTS

ABSTRACT

A class of novel benzo( b) pyrylium dye salts having a partially saturated, bicyclic ring system fused thereto is described.

111% fiates te Grisdafie 1 Sept. 26, 1972 [54] BENZO[b]PYRYLIUM DYE SALTS [5 6] References Cited [72] Inventor: PN|$iCk J- Grisdale, ROChCStfl, UNITED STATES PATENTS 3,3l4,975 4/1967 Jurd ..260/345.2 [73] Assignee: Eastman Kodak Company, Rom 3,554,745 1/1971 Van Allan ..260/345.2

ester ,N.Y. P J h M rimary Examinero 11 .Ford [22] March 21970 Attorney-W. H. J. Kline, Paul R. Holmes and J. Wil- [21] Appl. No.: 15,832 liam Berkstresser [52] US. Cl. ..260/345.2, 252/501, 96/89 ABSTRACT [51] Int. Cl. ..C07d 7/24 [58] Field of Search ..260/345.2 A class bemwmrylum dye salts havmg a partially saturated, bicyclic ring system fused thereto is described.

4 Claims, No Drawings BENZO/[BlPYRYLHUM DYE SALTS This invention relates to a novel class of benzo[b] pyrylium dye salts and in particular to such dyes having a partially saturated, bicyclic ring system fused thereto.

Compounds of the hereinafter described benzo[blpyrylium dye salts with partially saturated bicyclic ring systems fused thereto are more rigid in configuration than pyrylium dyes not containing this fused configuration. Such dye salts have a utility for sensitization of photoconductors and electrophotographic systems, as well as for other light sensitive systems. Further such dyes are unusually well suited for dye laser applications.

It is therefore an object of this invention to provide novel pyrylium dyes as hereinafter described having the sensitizing and lasing ability mentioned.

The compounds of the present invention have a structure conforming to the following general formula:

, while the remaining R R R, and R groups are hydrogen atoms; n is an integer from 1 to 4; and X is an acid anion such as halide, perchlorate, tetrafluoroborate, sulfate, bromate, carbonate, periodate, alkylsulfonate, arylsulfonate, and the like.

Compounds having the hereinbefore described general formula can be prepared by the reaction of an orthohydroxy aromatic aldehyde with a cyclic benzo ketone in the presence of acetic acid and a stream of hydrogen chloride gas. Generally, perchlorate acid is also added to the reaction mixture to facilitate isolation of the reaction product as the perchlorate salt which precipitates from the reaction mixture. The general preparation is illustrated by the following reaction R4 CHO R3 -OH 2 0111) HOAc, H01 gas F H0104 CH2 EXAMPLE 1 l 2, 1 B-Dihydrol 0-methoxy-dibenzo[ a,h] xanthylium perchlorate having the following structure is prepared by mixing 0.1 mole of 2-hydroxy-lnaphthaldehyde with 0.1 mole of 6-methoxy-ltetralone. The product was recrystallized from acetonitrile in a 42 percent yield at a melting point range of 272 to 275 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 64.0/64.4; H 4.1/4.4; Cl 8.6/8.5.

EXAMPLE 2 lO-methoxyl 2H-indeno[ 3 ,2-b] -naphtho[ l ,2- e ]pyrylium perchlorate having the following structure is prepared by mixing 0.1 mole of 2-hydroxy-lnaphthaldehyde with 0,1 mole of 5-methoxy-l-indanone. The product was recrystallized from acetic acid in a 55 percent yield at a melting point range of 283 to 285 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 63.2/629; H 3.8/4.1; Cl 8.9/9.1.

EXAMPLE 3 l ,2-dihydro-4-methoxy-benzo[c]xanthylium perchlorate having the following structure OCH:

EXAMPLE 4 Benzocyclohept[5,4-b]-naphtho[ l ,2-e]pyrylium perchlorate having the following structure is prepared by mixing 0.1 mole of 2-hydroxy-lnaphthaldehyde with 0.1 mole of benzocyclo-heptan-lone. The product was recrystallized from acetonitrilelacetic acid 121 in an 85 percent yield at a melting point range of 250 to 251 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 66.6/66.5; H 4.3/3.9; Cl 8.9/8.9.

EXAMPLE 5 l2H-indeno[ 3,2-b]naphtho-[ l,2-e]pyrylium perchlorate having the general structure is prepared by mixing 0.1 mole of 2-hydroxy-lnaphthaldehyde with 0.1 mole of l-indanone. The product was recrystallized from acetonitrile/acetic acid 1:] in an 82 percent yield at a melting point range of greater than 300 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 65.2/65.0; H 3.5/3.7; Cl 9.6/9.8.

EXAMPLE 6 12,1 3-dihydrodibenzo[a,h]-xanthylium perchlorate having the general structure is prepared by mixing 0.1 mole of 2-hydroxy-lnaphthaldehyde with 0.1 mole of l-tetralone. The product was recrystallized from acetonitrile/acetic acid 121 in a 68 percent yield at a melting point range of 280 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 65.8/66.1; H 3.9/4.1; Cl 9.3/9.4.

EXAMPLE 7 8-methoxy-l0H-indeno-[2,3-e]benzo[b]pyrylium perchlorate having the general structure is prepared by mixing 0.1 mole of salicylaldehyde with 0.1 mole of S-methoxy-l-indanone. The product was recrystallized from acetonitrile in a 72 percent yield at a melting point range of 244 to 245 C. The elemental analysis comparing the calculated amounts/amounts found, showed the following: C 58.5/582; H 3.8/4.0; Cl 10.2/10. l.

The hereinbefore described class of compounds are useful as sensitizers for electrophotographic systems as demonstrated by the following results.

The compound of Example 2, l0-methoxy-l2H-indeno[3,2-b]-naphtho[ l,2-e]pyrylium perchlorate and the compound of Example 3, 1,2-dihydro-4-methoxybenzo[c]xa.nthylium perchlorate were used to sensitize photoconductive coatings containing triphenylamine and 4,4'-bis(diphenylamino)chalcone respectively. The following table indicates that the photoconductors in conjunction with the compounds in a Vite] PElOl a polyester resin sold by the Goodyear Tire Company comprising poly(4,4-isopropylidene-bis-phenyleneoxyethylene-co-ethylene terephthalate), matrix produce photoconductive compositions having useful electrical H and D shoulder and toe speeds. The Vitel binder is generally used with 20 percent by weight of the photoconductor and 0.8 percent by weight of sensitizer compound.

amino(chalcone We claim:

1. IO-methoxyl 2H-indeno[ 3,2-b]-naphtho[ l ,2- e]pyrylium perchlorate.

2. Benzocyclohept[ 5,4-b]-naphtho[ l,2-e]pyrylium perchlorate.

3. l2H-indeno[ 3 ,2-b]naphtho-[ 1,2-e pyrylium perchlorate.

4. 8-methoxyl 0H-indeno-[ 2,3-e] benzo[ b] pyrylium perchlorate. 

2. Benzocyclohept(5,4-b)-naphtho(1,2-e)pyrylium perchlorate.
 3. 12H-indeno(3,2-b)naphtho-(1,2-e)pyrylium perchlorate.
 4. 8-methoxy-10H-indeno-(2,3-e)benzo(b)pyrylium perchlorate. 